JPH0827214A - Method for producing hydrogel, heavy metal ion adsorbent, dye adsorbent, microbial carrier and enzyme immobilizing carrier - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] A method for easily producing a hydrogel without requiring complicated operations and without using a large-scale apparatus, and a heavy metal ion adsorbent and a dye comprising the hydrogel. Provide an adsorbent, a microbial carrier, and an enzyme immobilization carrier. Constitution: An aqueous solution of a polymer having a repeating unit composed of a cationic group represented by the following formulas (1) and / or (2) is brought into contact with an alkaline aqueous solution to cause precipitation to form a hydrogel, and the hydrogel. Can be used as a heavy metal ion adsorbent, a dye adsorbent, a microbial carrier, an enzyme immobilizing carrier, and the like. (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and X ⁻ represents an anion.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydrogel having an amidine structure, a heavy metal ion adsorbent, a dye adsorbent,
The present invention relates to a microbial carrier and an enzyme immobilizing carrier.

[0002]

2. Description of the Related Art Hydrous gels containing a cationic dissociative group have been conventionally used as adsorbents, adsorbents for anionic organic substances, adsorbents for cells, cells and drugs, carriers for immobilized enzymes, fluidized bed ions. It is used in various applications such as exchange resins, fluid carriers for biological treatment equipment, and water-absorbent resins. As the hydrogel used for such a purpose, a cationic resin having a structure in which polyvinylamines such as polyvinylamine or polyisopropenylamine useful as a chelate resin are cross-linked (JP-A-61-44902), Polyvinylamines useful as basic anion exchange resins or chelating resins, or polyvinylamines such as polyisopropenylamine, which are crosslinked and spherically insolubilized (JP-A-61-51006). Highly cross-linked polyvinylamine (Japanese Patent Laid-Open No. 61-51007), a polymer using dialkylaminomethacrylate or a quaternary compound thereof as a monomer (Japanese Laid-Open Patent Publication No. 1-269493), vinyl pyridine, and other crosslinkable polymers. Cohesion, basic polymorphism obtained by processing chitin present in the crust of crabs and shrimps Chitosan solidified particles obtained by the acidic aqueous solution of chitosan is added dropwise to the aqueous alkaline solution medium (JP 62
No. 288601) is known. The production of these hydrogels is generally performed in a dispersion medium using an organic solvent in the presence of a cross-linking agent, and the production thereof has the drawback of requiring complicated operations and large-scale equipment. ,
On the other hand, it is difficult to stably obtain a large amount of a raw material for a natural product such as chitosan, which is expensive.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily and economically producing a hydrogel without the need for complicated operations and without using a large-scale apparatus, and its method. It is intended to provide a heavy metal ion adsorbent, a dye adsorbent, a microbial carrier and an enzyme immobilizing carrier, which are composed of a hydrogel.

[0004]

Means for Solving the Problems In view of the above problems, the inventors of the present invention have conducted extensive studies, and as a result, by contacting an aqueous solution of a specific cationic polymer compound having an amidine structure with an alkaline aqueous solution, It was found that a hydrogel can be easily produced, and the present invention has been accomplished.

The invention of claim 1 of the present invention is represented by the following formula (1):
A hydrogel characterized in that an aqueous solution of a polymer having a repeating unit of a cationic group represented by (Chemical Formula 3) and / or (2) (Chemical Formula 4) is brought into contact with an alkaline aqueous solution to cause precipitation and molding. Is a manufacturing method.

[0006]

Embedded image

[0007]

[Chemical 4]

(In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X ⁻ represents an anion.)

The invention of claim 2 of the present invention comprises 10 to 80 mol% of a repeating unit comprising a cationic group represented by the formula (1) and / or (2) of claim 1 and contains a cyano group. 1 to 1 of a polymer containing 10 to 60 mol% of a group
The method for producing a hydrous gel according to claim 1, wherein a 50 wt% aqueous solution is brought into contact with an alkaline aqueous solution to precipitate and mold the aqueous gel.

The invention according to claim 3 of the present invention comprises a crosslinking agent capable of reacting with active hydrogen in the molecule of the polymer in the aqueous solution and / or alkaline aqueous solution of the polymer according to claim 1 or 2. The method for producing a hydrous gel according to claim 1 or 2, wherein the method comprises coexisting.

The invention of claim 4 of the present invention is the method for producing a hydrogel according to any one of claims 1 to 3, wherein the pH of the alkaline aqueous solution of claim 1 is 11 or more. .

The invention according to claim 5 of the present invention is the method for producing a hydrogel according to any one of claims 1 to 3, characterized in that the pH of the alkaline aqueous solution according to claim 1 is 12 or more. .

The invention of claim 6 of the present invention is a method for producing a hydrogel, which comprises immersing the hydrogel of claim 3 in an acid aqueous solution to control the swelling property of the hydrogel.

The invention according to claim 7 of the present invention is characterized in that the aqueous acid solution according to claim 6 is an aqueous solution of at least one polybasic acid selected from sulfuric acid, phosphoric acid, boric acid and carbonic acid. Item 6. A method for producing a hydrous gel according to item 6.

The invention of claim 8 of the present invention is characterized in that the aqueous acid solution of claim 6 is an aqueous solution of at least one monobasic acid selected from hydrochloric acid and acetic acid. Is a manufacturing method.

The invention of claim 9 of the present invention is the invention of claims 1-8.
It is a heavy metal ion adsorbent characterized by comprising the hydrous gel described.

The invention according to claim 10 of the present invention includes claims 1 to 1.
A dye adsorbent characterized by comprising the hydrogel according to item 8.

The invention of claim 11 of the present invention is defined by claims 1 to 1.
8. A microbial carrier characterized by comprising the hydrogel according to item 8.

The invention of claim 12 of the present invention is the same as claims 1 to 1.
An enzyme-immobilizing carrier comprising the hydrogel according to item 8.

As the water-soluble polymer compound capable of producing a hydrogel by the method of the present invention, a water-soluble polymer compound having the repeating unit (amidine unit) represented by the above (1) and / or (2), preferably Can have 10 to 90 mol% of the above unit (amidine unit), more preferably 10 to 80 mol% of the above unit (amidine unit) and 10 to 60 mol% of a cyano group.

The above-mentioned cationic polymer having an amidine structure is sold in large quantities as a polymer flocculant as a wastewater treatment or a sludge dehydration agent, and the hydrogel of the present invention can be produced using it. The manufacturing method is not particularly specified. However, in general, a copolymer of an ethylenically unsaturated monomer having a primary amino group or a substituted amino group capable of forming a primary amino group by a conversion reaction and a nitrile of acrylonitrile or methacrylonitrile is produced, and further It can be produced by a method of reacting a cyano group in the copolymer with a primary amino group to form an amidine.

The above ethylenically unsaturated monomer has the general formula CH ₂ ═CR ² —NHCOR ³ (wherein R ² represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom). The compound represented by In the copolymer, a substituted amino group derived from such a compound is easily converted to a primary amino group by hydrolysis or alcoholysis. Further, the primary amino group reacts with an adjacent cyano group to form an amidine. Examples of the compound include N-vinylformamide (R ² = H,
R ³ = H), N-vinylacetamide (R ² = H, R ³
= Me) and the like.

The polymerization molar ratio of these ethylenically unsaturated monomers and nitriles is usually from 30:70 to 70:30.
However, if desired, it is also possible to employ a polymerization molar ratio outside this range, for example, a polymerization molar ratio with a higher proportion of ethylenically unsaturated monomers.

As a method of copolymerizing the ethylenically unsaturated monomer and the nitriles, a usual radical polymerization method is used, and any of aqueous solution polymerization, bulk polymerization, aqueous solution precipitation polymerization, suspension polymerization, emulsion polymerization and the like is used. be able to. When polymerized in a solvent, the raw material monomer concentration is usually 5 to 80.
%, Preferably 20 to 60% by weight. Although a general radical polymerization initiator can be used as the polymerization initiator, an azo compound is preferable, and a hydrochloride of 2,2′-azobis-2-amidinopropane and the like are exemplified.
In addition, the polymerization reaction is generally carried out under an inert gas flow of 30 to
It is carried out at a temperature of 100 ° C. The obtained copolymer can be used as it is or after being diluted, that is, in the form of a solution or suspension for the amidination reaction. Also,
It is also possible to desolvate and dry the copolymer by a known method to separate the copolymer as a solid, and then use the solid for the amidineization reaction.

In the amidination reaction, when the N-vinylamide compound represented by the above general formula is used as the ethylenically unsaturated monomer, the substituted amino group of the copolymer is converted into a primary amino group and then produced. The cationic polymer according to the present invention can be produced by a two-step reaction in which a primary amino group is reacted with a cyano group adjacent thereto to form an amidine structure. Then, preferably, the copolymer is heated in a water or alcohol solution in the presence of a strong acid or a strong base to form an amidine structure in one step. Also in this case, it is considered that a primary amino group is first generated as an intermediate structure.

The specific conditions of the reaction are, for example, usually 0.9 to 0.9 with respect to the substituted amino group of the copolymer.
Add 5.0 times, preferably 1.0 to 3.0 times equivalent of a strong acid, preferably hydrochloric acid, and heat at a temperature of usually 80 to 150 ° C, preferably 90 to 120 ° C, usually for 0.5 to 20 hours. Thereby, a cationized polymer having an amidine unit can be obtained. Generally, the higher the equivalent ratio of the strong acid to the substituted amino group and the higher the reaction temperature, the more amidination proceeds. In addition, in the case of amidination, 10% by weight or more, preferably 20% by weight or more of water is usually present in the reaction system with respect to the copolymer used in the reaction.

The cationic polymer according to the present invention is most typically prepared by copolymerizing N-vinylformamide and acrylonitrile according to the above-mentioned explanation, and the resulting copolymer is usually suspended in water. It is prepared by heating in the presence of hydrochloric acid as a liquid to form an amidine unit from a cyano group adjacent to a substituted amino group. Then, by selecting the molar ratio of N-vinylformamide and acrylonitrile to be subjected to copolymerization and the amidation conditions of the copolymer, it is possible to produce cationic polymers of various compositions.

An aqueous solution of 0.5% by weight or more and less than 50% by weight, preferably 1% by weight or more and less than 20% by weight of the water-soluble cationic polymer compound thus obtained is prepared,
By contacting with an alkaline aqueous solution having a pH of 11 or more, preferably pH 12 or more, more preferably pH 12.5 or more, dissociation of the primary amino group of the water-soluble cationic polymer compound is suppressed, and the polymer compound becomes a water-insoluble resin, A hydrous gel is formed. This phenomenon is because the amino group having an amidine structure is suppressed from being dissociated at a pH of 10.5 or higher and is hydrophobized.

This hydrogel can be prevented from deteriorating by washing with water to remove the alkaline component in the gel. By holding it in the presence of an alkaline component, the cyano group and amidine unit in the polymer are hydrolyzed and converted into a carboxyl group, forming an amphoteric hydrogel having an anionic group and a cationic group in the resin. It Depending on the application, in order to actively promote this hydrolysis, soak in an alkaline solution for a long time, or in an alkaline solution,
By heating, it is possible to form a hydrogel in which a large number of carboxyl groups coexist in the molecule.

Usually, in order to suppress this hydrolysis, neutralization with an acid or washing with an aqueous acid solution is carried out.
The obtained water-containing gel recovers the original water solubility of the polymer compound of the gel constituent unit near neutrality, absorbs water and swells,
Eventually it will dissolve and will not stay in shape. As a method for solving such a problem, a functional group that forms a covalent bond by a reaction with an amino group or a cyano group of a polymer compound in a polymer aqueous solution to be prepared at the time of producing a hydrogel or in an alkaline aqueous solution to be contacted is used. A method is used in which a cross-linking agent having two or more molecules in one molecule is allowed to coexist, and then an aqueous solution of a polymer is brought into contact with an aqueous alkali solution. The hydrogel thus formed can form a stable water-insoluble gel without being redissolved even when neutralized with an acid. When a polybasic acid such as sulfuric acid or phosphoric acid is used as the acid used for neutralization, the amino group in the molecule forms a sulfate salt or a phosphate salt, and a hydrogel having a low swelling property can be formed. When a monobasic acid such as hydrochloric acid or acetic acid is used for neutralization, a hydrated gel having a swelling ratio of 100 times or more can be obtained by adjusting the amount of the crosslinking agent used.

As specific examples of the cross-linking agent to be used, diformylalkanes such as formaldehyde, acetaldehyde, glyoxal, malonaldehyde and glutaraldehyde can be used.
A hydrogel can also be formed by using a crosslinking agent having two or more functional groups capable of reacting with a primary amino group or a cyano group to form a covalent bond in one molecule. When N-vinylformamide and N-vinylacetamide monomers coexist in the synthesized polymer, these monomers hydrolyze to form acetaldehyde, which functions as a crosslinking agent. In some cases, it may be unnecessary to add a crosslinking agent.

The hydrogel of the present invention can be obtained by bringing an aqueous solution of a polymer compound having an amidine structure into contact with a basic aqueous medium. In this case, the concentration of the aqueous solution of the polymer compound prepared is 0.5. The concentration is selected from the range of weight% or more and less than 50% by weight, preferably 1% by weight or more and less than 20% by weight, and the concentration is determined by the water content ratio and gel strength of the finally obtained hydrous gel. Generally, the higher the aqueous solution concentration of the polymer compound to be contacted, the lower the water content ratio and the higher the gel strength. Conversely, the lower the concentration,
Since the viscosity of the polymer solution decreases and the polymer solution disperses in the alkaline solution due to the impact on the liquid surface when contacting with the alkaline aqueous solution, it becomes difficult to form a hydrogel. However, it becomes difficult to produce a hydrogel at a low concentration. Further, if the molecular weight is too high, when a hydrogel is formed by dropping or extruding into an aqueous alkaline solution, the aqueous polymer solution has spinnability, and the resulting hydrogel is distorted in shape or filamentous in the hydrogel. A protrusion is formed.

If the aqueous solution of the polymer is too viscous, it is diluted appropriately, but an oxidizer is added to cut the molecules to reduce the molecular weight, or salts such as sodium chloride, sodium acetate and potassium chloride are added. It is also possible to reduce the apparent viscosity by adding.

As the basic compound used in the basic medium used to form the hydrous gel, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium carbonate and the like are used, but water is usually used in view of handling and price. Sodium oxide is used. Coexistence of salts such as ammonium sulfate, crystallization, sodium chloride, and potassium chloride in the basic medium used can facilitate formation of a hydrogel and reduce the water content of the hydrogel.

The concentration of the basic compound used in the basic medium varies depending on the total amount of the polymer compound to be contacted with it, but it is usually used in the range of 1% by weight to 2% by weight. But it doesn't matter. However, the alkali in the basic medium is consumed by bringing the aqueous polymer solution into contact therewith, and therefore it is necessary to replenish the basic compound in producing the hydrogel. The specific gravity of the aqueous solution of the polymer compound to be contacted is extruded into a basic dispersion medium, or
When forming a hydrogel by dripping, it is desirable to adjust the specific gravity to be equal to or higher than the specific gravity of the basic dispersion medium, and in order to adjust the specific gravity, salt, crystallization, etc. in an aqueous solution of the dissolved polymer compound Inorganic water-soluble electrolytes and water-insoluble powders such as calcium carbonate, talc, activated clay, powdered ferrite and powdered activated carbon are allowed to coexist.

When producing a hydrogel according to the method of the present invention, it is also possible to coexist with an enzyme, a bacterium and the like in an aqueous solution of a polymer compound, and fix them entrapped and used as a carrier for a bioreactor. . Alternatively, the hydrous gel obtained by the method of the present invention can be contacted with an enzyme solution to adsorb the enzyme to produce an immobilized enzyme. In addition, by releasing an antibiotic, a bactericidal agent, an antibacterial agent or the like in a polymer solution and then producing a hydrogel by the method of the present invention, it is possible to impart a sustained-release property to these agents. Further, powdered activated carbon, zeolite, after dispersing an inorganic powder such as ferrite in an aqueous polymer solution, by producing a hydrogel by the method of the present invention, it is possible to adjust the specific gravity of the hydrogel at the same time, obtain The hydrated gel thus obtained can have various functions.

In producing a hydrous gel by the method of the present invention, usually, a spherical hydrous gel can be formed by dropping an aqueous solution of a polymer compound using a metering pump or the like. The particle size of the hydrogel can be changed by the viscosity of the polymer solution, the dropping rate, the diameter of the dropping port, and the like. Further, by extruding the aqueous polymer solution into the alkaline aqueous solution, a rod-shaped or thread-shaped hydrogel can be formed. In addition, various hydrogel composites can be formed by impregnating the polymer aqueous solution used in the present invention into a porous material, a fiber assembly, and the like, and then contacting it with an alkaline solution.

The hydrogel obtained by the present invention can be used in various industrial fields, and the following specific examples can be given. 1) Use as a fluid carrier in a biological fluidized bed wastewater treatment method. 2) Application to wastewater treatment systems as an adsorbent for anionic organic substances such as dyes, surfactants, lignin and humic substances. 3) Application to bioreactors by entrapping or adsorbing and fixing physiologically active substances such as microorganisms and enzymes. 4) Since the hydrogel having the structure of the present invention has an excellent effect as a chelate resin, water containing metal ions is passed through a column packed with the hydrogel of the present invention or in a solution containing metal ions of the present invention. By immersing the hydrous gel, the metal ions in the solution can be removed and concentrated. If a crosslinked hydrous gel is used, it is also possible to immerse the adsorbed metal ions in a mineral acid, recover the gel, and repeatedly use the regenerated gel.

[0039]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples, "%" means "% by weight" unless otherwise specified.

[Cationic Polymer Production Method] A 50 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a condenser tube contained acrylonitrile and N-vinyl containing acrylonitrile in a mole fraction shown in Table 1. 6.0 g of a mixture of formamide and 34.0 g of demineralized water were added. In a nitrogen gas stream, the temperature was raised to 60 ° C. with stirring and then 10
% 0.12 g of 2,2'-azobis-2-amidinopropane dihydrochloride aqueous solution was added. After stirring and holding at 45 ° C. for 4 hours, the temperature was raised to 60 ° C. and further holding for 3 hours to obtain a suspension in which the polymer was precipitated in water. 2 water in the suspension
0 g was added, and then 2 to the formyl group in the polymer.
An equivalent amount of concentrated hydrochloric acid was added, and the mixture was kept at 100 ° C. for 4 hours with stirring to amize the polymer. The resulting polymer solution was added to acetone to cause precipitation, which was vacuum dried to prepare solid polymers A to E as prototypes. The polymer E was obtained by polymerizing without using acrylonitrile and performing the same reaction. Compositions and reduced viscosities of the polymers A to E were measured by the following methods. The results are summarized in Table 1.

[Method of Analyzing Composition] The composition of each raw material polymer before amidation was determined by ¹³ C-NMR spectrum ( ¹³ C-
It was calculated from the integrated value of the absorption peak corresponding to each monomer unit of the magnetic resonance spectrum). The compositions of Polymers A to E after amidineization were calculated from the integrated values of absorption peaks corresponding to each repeating unit in the ¹³ C-NMR spectrum. Note that the repeating units (1) and (2) are not distinguished,
It was calculated as the total amount. The repeating units (8) and (9) were also determined as the total amount without distinction.

Further, repeating units (1) and (2),
The absorption peaks of (6) and (8) and (9) are 170 to 1
Since they were found at very close positions around 85 ppm, the structure corresponding to each absorption peak was assigned by the following method. That is, the weight balance was confirmed by elemental analysis of the polymer and measurement of the water content, and further, ¹³ C-NMR of the polymer was confirmed.
In addition to the spectrum, an IR spectrum is also measured, and a method for comparing and examining the spectrum of the polymer and the spectrum of a known compound having an amidine group, an amide group, a lactam group, etc. in detail is adopted.

[Measurement of Reduced Viscosity] For the polymers A to E,
It was measured as a solution of 0.1 g / 100 ml in 1 N saline at 25 ° C. using an Ostwald viscometer.

[0044]

[Table 1]

Example 1 5 g of the polymers A to D of the prototype were added to 85 g of distilled water and mixed and stirred to dissolve the polymer, and then 10 g of salt and 25% of glutaraldehyde were added.
Add 0.1 g of the aqueous solution and stir well. This polymer solution was used for 10 minutes per minute using an Atto tubing pump.
Drop at a rate of milliliter into 500 ml of a 2% caustic soda solution. In this case, the 2% caustic soda solution was stirred with a stirrer at 300 rpm, and the height of the dropping portion and the surface of the caustic soda was maintained at about 2 cm. After the dropping is completed, the stirring is continued for another 30 minutes, and then the pH of the caustic soda solution is adjusted to 7.5 with sulfuric acid. The water-containing gels (Sample-1 to Sample-4) obtained by filtering this through a screen were washed with pure water, and then the average particle size and water content ratio were measured. The results are shown in Table 2. The water content was calculated by the following formula.

(Comparative Example 1) For the purpose of comparison, an attempt was made to produce a hydrous gel by repeating the same procedure as in Example 1 except that the polymer E of the prototype example having no amidine structure was used. However, the polymer dissolved in the caustic soda solution. Table 2 shows the results.

[0047]

[Table 2]

Example 2 5 g of the polymer B of the prototype example was added to 85 g of distilled water and mixed and stirred. After the polymer was dissolved, 10 g of salt was added and mixed and stirred until completely dissolved. 1% glutaraldehyde was added to this solution.
After adding and mixing in the proportions shown in (1), the mixture is dropped into a caustic soda solution and granulated in the same manner as in Example 1. After holding this granulated product in an alkaline atmosphere at 30 ° C. for 1 hour, half the amount was neutralized with hydrochloric acid, and the other half was neutralized with sulfuric acid to adjust the pH.
Adjust to 7. This is separated by filtration, and each is placed in pure water.
After soaking for a period of time, the water-containing gel (Sample-5
~ Measure the weight of Sample-8). Then, the hydrous gel is dried at 105 ° C. for 20 hours, the weight is measured, and the swelling ratio is calculated by the following formula. The results obtained are summarized in Table 3.

Comparative Example 2 A sample operated in the same manner as in Example 1 except that 1% glutaraldehyde was not added to the above solution, was dissolved during neutralization and did not form a hydrous gel. It was The results are shown in Table 3.

[0050]

[Table 3]

(Example 3) 10 g of the polymer C of the prototype example, 90 g of distilled water, and powdered iron tetroxide (particle size: 100 μm or less) 3
After mixing and stirring 0 g to make a uniform slurry, 2 g of a 10% acetaldehyde solution was added, and then dropped into a 2% caustic soda solution by the same operation as in Example 1. After the dropping was completed, the pH of the caustic soda solution was adjusted to 7.5 with sulfuric acid and then filtered off, whereby a hydrous gel containing ferric tetroxide could be produced. The apparent specific gravity of the obtained hydrous gel in water is 1.54, and the average particle size is 2.3 mm.
Met. The water content ratio of this water-containing gel was 215%.
This hydrogel can be separated from the liquid by a magnet.

Example 4 250 g of the hydrogel of Sample-2 produced in Example 1 was used to obtain a diameter of 40 mm and a height of 300.
mm column is packed and the copper chloride concentration is 20 from the bottom of the column.
A mg / liter solution was passed at a flow rate of 10 ml / min, and the copper ion concentration of the treated water flowing out from the upper end was measured by an atomic absorption photometer (manufactured by Shimadzu Corporation). The copper ion concentration of the treated water after passing 200 liters is 0.08 mg /
It was liter.

Example 5 250 g of the hydrogel of Sample-3 produced in Example 1 was used to obtain a diameter of 40 mm and a height of 300.
40 mm of Alfanol Fast Scarlet BL (manufactured by Hoechst) from the lower end of the column.
A solution having a concentration of 0 mg / liter was passed through a tubing pump (manufactured by Ato) at a flow rate of 2 ml / min,
The residual dye concentration of the effluent water from the upper end is measured using an absorptiometer, and the total amount of dye adsorbed by the hydrogel when the residual dye concentration becomes 20% or less of the raw water is calculated. Table 4 shows the water flow rate, residual dye concentration and dye adsorption integrated amount. From the results of Table 4, the dye adsorption capacity of this gel is 59.3 mg / g.

[0054]

[Table 4]

(Example 6) In the aerobic fluidized bed type biological treatment apparatus provided with an air diffuser, an air lift pipe, etc. for flowing the carrier in the aeration tank, the hydrous gel (sample- 4) was applied as a carrier. The water-containing gel was placed in an aeration tank having the structure shown in FIG. 1 and having a volume of 1 liter.
00g and 9 aeration tank sludge (sludge concentration 4000mg / l) obtained from activated sludge treatment site of sewage treatment plant
After injecting 00 ml and aerating for 24 hours,
Artificial wastewater (oxidized starch 250 mg / liter, peptone 2
50 mg / liter, potassium phosphate 15 mg / liter, ferrous sulfate 1 mg / liter, magnesium sulfate 1
mg / liter, calcium chloride 1 mg / liter) was quantitatively supplied into the aeration tank at a rate of 3 liters / day by a perista pump (manufactured by Ato Co., Ltd.). The temperature in the aeration tank during water flow was maintained at 25 ° C. The BOD of this artificial wastewater is 390 mg / liter. The quality of the supernatant water of the treated water was analyzed 1 week, 2 weeks, and 4 weeks after the start of water flow.
The obtained results are summarized in Table 5.

Comparative Example 3 The same test as in Example 6 was carried out without adding a carrier for comparison. The obtained results are summarized in Table 5.

Comparative Example 4 For comparison, 200 g of polystyrene beads having an average particle size of about 1 mm was used as a carrier.
The same test as in Example 6 was performed. The obtained results are summarized in Table 5.

[0058]

[Table 5]

As is clear from the results shown in Table 5, the activated sludge could not be retained in the aeration tank unless the carrier was added (Comparative Example 3), and the treatment was impossible. However, the hydrogel of Example 6 (Sample-
In the aeration tank to which 4) was added, activated sludge was fixed on the surface of the hydrous gel, and after 2 weeks, formation of a microbial film was confirmed on the surface of the hydrous gel, and the treated water quality was also good. Even with the polystyrene beads used for comparison as a carrier (Comparative Example 4), a slight microbial membrane formation was observed after 4 weeks, and the treated water quality was also improved, but compared to the hydrous gel of the present invention, The formation speed is inferior and the rise of the process is slow.

(Example 7) 10 g of each of the hydrous gels of Sample-2 and Sample-3 produced in Example 1 were sampled,
The mixture is suspended and dispersed in 200 ml of 0.05 mol Tris-hydrochloric acid buffer solution (pH 8.0) and then filtered. Then, this was immersed in 100 ml of a 0.05 mol phosphate-citrate buffer solution, 20 ml of an invertase solution (manufactured by Sankyo Co., Ltd.) was further added, and immobilization was performed while stirring at room temperature for 3 hours. The thus-obtained enzyme-immobilized hydrogel was diluted with sodium borate-hydrochloric acid buffer having a concentration of 0.05 mol containing 0.6% of glutaraldehyde.
After soaking for a period of time, this is separated by filtration, suspended and dispersed again in 1 liter of 0.05 mol Tris-hydrochloric acid buffer, and filtered, and the weight of the obtained enzyme-immobilized hydrous gel is measured. 10% solution 1 of sucrose in which the obtained immobilized enzyme was dissolved in a citrate-phosphate buffer solution (pH 4.2) having a concentration of 0.05 mol.
Add to liter and react at 40 ° C. for 60 minutes,
The total amount of reducing sugars formed was determined by the methylene blue method, and Table 6 shows the amount of sucrose decomposed by 1 g of the enzyme-immobilized hydrous gel per hour.

(Comparative Example 5) For Comparative Example, a commercially available strong basic ion exchange resin Amberlite IRA-90X (manufactured by Organo) was used and the same operation as in Example 7 was carried out to decompose saccharose per 1 g of the resin. The amount was determined and is shown in Table 6.

[0062]

[Table 6]

(Example 8) 10 g of the hydrogel (Sample-2) using the polymer B produced in Example 1 was washed with water, filtered, and 0.05 ml of sodium borate-hydrochloric acid buffer solution ( After immersing in (pH 6.0) for 10 minutes,
Filter again. This is put into 100 ml of a 3-fold diluted solution of glucose isomerase (manufactured by Nagase) that has been dialyzed, gently stirred at room temperature, and then filtered. The thus obtained enzyme-immobilized hydrogel was immersed in a sodium borate-hydrochloric acid buffer solution having a concentration of 0.05 mol containing 0.6% glutaraldehyde for 1.5 hours. This hydrogel and glutaraldehyde-untreated hydrogel were each
After immersing in 1 liter of 0% saline and stirring for 1 hour, the mixture was filtered, washed with water, and the ability to convert each glucose into fructose was compared. The glucose conversion ability is based on the following method. The obtained enzyme-immobilized hydrogel was added to 1 liter of a 40% glucose solution dissolved in a phosphate buffer having a concentration of 0.1 mol, and the mixture was allowed to stand at 60 ° C. for 1 hour.
After reacting for a time, the amount of fructose formed as a result is changed to H.
The amount of glucose converted to fructose per 1 g of hydrous gel (glucose conversion amount) was determined by the PLC method. The results are shown in Table 7.

[0064]

[Table 7]

From the results shown in Table 7, it is understood that an enzyme-immobilized hydrous gel in which the enzyme does not come off can be formed by adsorbing the enzyme on the hydrous gel of the present invention and then treating with glutaraldehyde.

[0066]

According to the method for producing a hydrous gel of the present invention, a hydrous gel can be easily produced without requiring a complicated operation and without using a large-scale apparatus. Since the hydrogel can be used as a heavy metal ion adsorbent, a dye adsorbent, a microorganism carrier, an enzyme immobilizing carrier, etc., it has a high industrial utility value.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the structure of an aeration tank.

[Explanation of symbols]

 1 Blower 2 Air diffuser 3 Carrier 4 Aeration tank 5 Sedimentation tank 6 Partition wall 7 Treated water 8 Partition wall 9 Artificial drainage

[Procedure amendment]

[Submission date] July 20, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

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Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and X ⁻ represents an anion.)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

(In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and X ⁻ represents an anion.)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Composition Analysis Method] The composition of each raw material polymer before amidation was calculated from the integral value of the absorption peak corresponding to each monomer unit of the ¹³ C-NMR spectrum ( ¹³ C-the magnetic resonance spectrum). The composition of each of the polymers A to E after amidation was calculated from the integrated value of the absorption peak corresponding to each repeating unit of the ¹³ C-NMR spectrum. The repeating units (1) and (2) were calculated as the total amount without distinction .

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[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

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The absorption peaks of the repeating units (1) and ( 2) and the absorption peaks of primary amines are 170 to 185.
Since they were found at extremely close positions around ppm, the structure corresponding to each absorption peak was assigned by the following method. That is, the weight balance was confirmed by elemental analysis of the polymer and measurement of the water content, and further the IR spectrum was measured in addition to the ¹³ C-NMR spectrum of the polymer, and the spectrum of the polymer and the amidine group, amide group and lactam were measured. It employs a method in which the spectrum of a known compound having a group or the like is compared in detail.

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Claims (12)

[Claims] 1. An aqueous solution of a polymer having a repeating unit consisting of a cationic group represented by the following formula (1) (Chemical formula 1) and / or (2) (Chemical formula 2) is brought into contact with an alkaline aqueous solution to cause precipitation. A method for producing a hydrogel, comprising: Embedded image Embedded image (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X ⁻ represents an anion.) 2. A repeating unit comprising a cationic group represented by the formula (1) and / or (2) according to claim 1 is contained in an amount of 10 to 80 mol% and a cyano group is included in an amount of 10 to 60 m.
The method for producing a hydrogel according to claim 1, wherein an aqueous solution of 1 to 50% by weight of a polymer containing ol% is brought into contact with an alkaline aqueous solution to precipitate and mold. 3. A cross-linking agent capable of reacting with active hydrogen in the molecule of the polymer is allowed to coexist in the aqueous solution and / or alkaline aqueous solution of the polymer according to claim 1 or 2. Item 1. The method for producing a hydrogel according to claim 1 or 2. 4. The pH of the alkaline aqueous solution according to claim 1.
Is 11 or more, The manufacturing method of the hydrous gel in any one of Claims 1-3 characterized by the above-mentioned. 5. The pH of the alkaline aqueous solution according to claim 1.
Is 12 or more, The manufacturing method of the hydrous gel in any one of Claims 1-3 characterized by the above-mentioned. 6. A method for producing a hydrogel, which comprises immersing the hydrogel according to claim 3 in an aqueous acid solution to control the swelling property of the hydrogel. 7. The hydrogel according to claim 6, wherein the aqueous acid solution is an aqueous solution of at least one polybasic acid selected from sulfuric acid, phosphoric acid, boric acid and carbonic acid. Method. 8. The method for producing a hydrous gel according to claim 6, wherein the acid aqueous solution according to claim 6 is an aqueous solution of at least one monobasic acid selected from hydrochloric acid and acetic acid. 9. A heavy metal ion adsorbent comprising the hydrogel according to claim 1. 10. A dye adsorbent comprising the hydrogel according to claim 1. 11. A microbial carrier comprising the hydrogel according to any one of claims 1 to 8. 12. An enzyme-immobilizing carrier comprising the hydrogel according to any one of claims 1 to 8.